Ink compositions and their preparation

ABSTRACT

An aqueous printing ink or its semiaqueous or substantially nonaqueous concentrates exemplified as comprising a substantially homogeneous system of the components: 
     (1) from about 4 to about 90 weight % of one or more polyester materials having an acid component of from about 75 to about 84 mole % isophthalic acid and conversely from about 25 to about 16 mole % 5-sodiosulfoisophthalic acid, and having a glycol component of from about 45 to about 60 mole % diethylene glycol and conversely from about 55 to about 40 mole % 1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof; 
     (2) from none to about 70 weight % of pigment material; 
     (3) from about 0.01 to about 90 weight % of water; and 
     (4) one or more acetylacetonates of the formula M[CH--(COCH 3 ) 2  ] n  wherein M is Al, Zr, Ni, Ca, V, or Fe, and n is the chemical valence of M, the weight ratio of polyester to total acetylacetonates being from about 10,000/1 to about 10/1.

This is a divisional of application Ser. No. 07/084,773, filed Aug. 13,1987, now U.S. Pat. No. 4,772,491.

TECHNICAL FIELD

This invention concerns pigmented and nonpigmented, aqueous inks andcoatings and their nonaqueous or semiaqueous concentrates, containingcertain insolubilizing agents and having greatly improved printing andcoating properties such as flow-out, print smoothness, transparency,gloss, color development, and the like, wherein the pigment carrier orbinder comprises water-dispersible polyester or polyester-amidematerial. The term "water-dispersible" includes water-dissipatable,water-soluble, aqueous suspension, colloidal dispersion or the like. Theinks find special utility for letter press, intaglio, gravure,flexographic and other printing processes adaptable to the use ofaqueous inks. The term "ink" is used herein in its broad sense asincluding the use thereof for coatings in all forms such as letters,patterns and coatings without design.

BACKGROUND OF THE INVENTION

The printing industry in general finds may applications for the use ofwater-based inks and overprint varnishes as a means of meetingincreasingly stringent solvent effluent regulations. Present daywater-based inks often fail to satisfy these regulations as well as thenecessary printability, stability, and performance properties requiredfor commercial inks. For example, the various ethyleneacrylic acidcopolymer salts of U.S. Pat. No. 3,607,813, the disclosure of which isincorporated herein by reference (for the printing process descriptionstherein), in addition to requiring complex polymer and ink preparations,lack in performance on certain substrates. Other such aqueous orsemiaqueous systems proposed for printing inks contain polymers such asstyrene-butadiene or polyacrylate latex systems but these systems alsohave serious drawbacks including being non-water dispersible after shortdrying periods which complicates equipment clean up. Other water solubleor dispersible polymers suggested for printing ink use are discussed inU.S. Pat. No. 4,072,644.

In the commercial use of polymeric coatings such as paints, inks, andthe like that are applied from water solutions or dispersion, it is aneconomic advantage to have a material that is initially resoluble orredispersable in water even after it has dried to a film. This allowsfacile water clean-up of coating and printing equipment and other itemssuch as mixing vessels and handling equipments such as sampling cups andviscosity measurement instruments. However, it is also an advantage ifthe resulting coating can be converted in a short time to a highlywater-resistant surface on the coated or printed product. Theseseemingly contradictory requirements are not well met by currentcommercial materials and post treatment techniques. The best resultspublished to date invovle pH change, i.e., evaporation of ammonia orsimilar base, to yield insoluble coatings, however, the pH adjustmentscan be a problem with a highly volatile base and odorous emissions andequipment corrosion often result.

It has now been discovered that far superior ink systems having thesedesirable properties can be prepared through the use of certainwater-insoluble metal chelates which are sequestered at a pH of fromabout 6.0 to about 8.0 in water dispersions of the water-dispersiblepolymers, and which then behave as stable, "sequestered" hydrophobes aslong as water is present. Evaporation of the water and subsequentholding and/or heating, usually as a part of the production drying,gives a highly water-resistant film which is essentialy otherwiseunchanged.

It is noted that the application of heat to a film of the ink,particularly to a film containing some water such as a freshly printedfilm, will enhance the insolubilizing action of the metal complexedacetylacetonates which enhancement is manifest in greaterinsolubilization. The heating is preferably at temperatures of fromabout 50° C. to about 100° C., for about 2.0 to about 40 seconds, andmost preferably of from about 70° C. to about 90° C. for about 4.0 toabout 10.0 seconds.

It is known that free multivalent cations will cause suchwater-resistance to develop in polymer films post-treated in separate,extrinsic operations with solutions containing multivalent cations (seedefensive publication T-949001); however, stable, water-insoluble metalchelates would not be expected to be sequesterable in such a system toprovide a highly convenient mechanism for insolubilization, much lessgive equivalent or superior water resistance upon drying.

The present invention, in addition to providing a unique ink systemhaving an early redispersable phase which can be rendered essentiallynondispersable, also provides marked improvements in the preparation,stability, and performance of water-based inks for printing and coating,particularly in regard to flow-out, color development and pick-up on theprinting rollers and other machine elements.

DESCRIPTION OF THE INVENTION

The invention is defined as a composition useful as an ink or useful forthe preparation of inks, comprising a substantially homogeneous systemof the components:

(1) from about 4 to about 90 weight % of polymeric material of at leastone linear water-dispersible polymer having carbonyloxy linking groupsin the linear molecular structure wherein up to 80% of the linkinggroups may be carbonylamido linking groups, the polymer having aninherent viscosity of from about 0.1 to about 1.0, preferably from about0.1 to about 0.5 measured in a 60/40 parts by weight solution ofphenol/tetrachloroethane at 25° C. and at a concentration of 0.25 gramof polymer in 100 mL of the solvent, the polymer containingsubstantially equimolar proportions of acid equivalents (100 molepercent) to hydroxy and amino equivalents (100 mole percent), thepolymer comprising the reaction products of (a), (b), (c), and (d) fromthe following reactants or ester forming or ester-amide formingderivatives thereof;

(a) at least one difunctional dicarboxylic acid;

(b) from about 4 to about 25 mole percent, based on a total of all acid,hydroxyl and amino equivalents being equal to 200 mole percent, of atleast one difunctional sulfomonomer containing at least one metalcationic group attached to an aromatic or cycloaliphatic nucleus whereinthe functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reactant selected from a glycol or amixture of a glycol and diamine having two --NRH groups, the glycolcontaining two --CH₂ --OH groups of which

(1) at least 15 mole percent based on the total mole percent of hydroxyor hydroxy and amino equivalents, is a poly(ethylene glycol) having thestructural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of from 2 to about 20, or

(2) of which from about 0.1 to less than about 15 mole percent based onthe total mole percent of hydroxy or hydroxy and amino equivalents, is apoly(ethylene glycol) having the structural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of between 2 and about 500, preferably between 2 andabout 200, and with the provision that the mole percent of saidpoly(ethylene glycol) within said range is inversely proportional to thequantity of n within said range; and

(d) from none to at least one difunctional reactant selected from ahydroxycarboxylic acid having one --C(R)₂ --OH group, an aminocarboxylicacid having one --NRH group, and an amino-alcohol having one --C(R)₂--OH group and one --NRH group, or mixtures of said difunctionalreactants;

wherein each R in the (c) or (d) reactants is a H atom or an alkyl groupof 1 to 4 carbon atoms;

(2) from none to about 70 weight % of pigment material;

(3) from about 0.01 to about 90 weight % of water; and

(4) one or more acetylacetonates of the formula M[CH--(COCH₃)₂ ]_(n)wherein M is a polyvalent metal and n is the chemical valence of M, theweight ratio of water-dispersible polymer to total acetylacetonatesbeing from about 10,000/1 to 10/1.

In the above polymeric material it is preferred that very minor, e.g.,less than about 10 mole % based on all reactants, of reactant (d) isemployed, that at least about 70 mole % of reactant (c) is glycol, andthat at least about 70 mole % of all the hydroxy equivalents is presentin the glycol.

The pigments useful in the present invention, in addition to thosespecifically identified below, include those described in NPIRI RawMaterials Data, Vol. 4, Pigments, Copyright 1983. Conventionaldispersing aids, biocides, defoamers and the like may be used in thepresent inks if desired for their known effects.

In a preferred embodiment of the invention, the water-dispersiblepolymeric material comprises (a) an acid component (moiety) of fromabout 75 to about 84 mole % isophthalic acid and conversely from about25 to about 16 mole % 5-sodiosulfoisophthalic acid, and (b) a glycolcomponent (moiety) of from about 45 to about 60 mole % diethylene glycoland conversely from about 55 to about 40 mole %1,4-cyclohexanedimethanol or ethylene glycol or mixtures thereof, andwherein the weight ratio of pigment material to said polymeric materialis from about 1/10 to about 2/1. With regard to this polymeric material,the term "moiety" as used herein designates the residual portion of thereactant acid or glycol which actually enters into or onto the polymerchain during the condensation or polycondensation reaction.

Further preferred embodiments of the invention are as follows:

(a) the inherent viscosity of the water-dispersible polymeric materialis from about 0.28 to about 0.38, the said acid component (moiety)comprises from about 80 to about 83 mole % isophthalic acid andconversely from about 20 to about 17 mole % 5-sodiosulfoisophthalicacid, and the said glycol component (moiety) comprises from about 52 toabout 56 mole % diethylene glycol and conversely from about 48 to about44 mole % 1,4-cyclohexanedimethanol;

(b) the pigment is one or a mixture of the following color indexmaterials according to their generic names: C.I. Pigment Yellow 17; C.I.Pigment Blue 27; C.I. Pigment Red 42:2; C.I. Pigment Red 81:1; C.I.Pigment Red 81:3; C.I. Pigment Red 81:x; C.I. Pigment Yellow 83; C.I.Pigment Red 57:1; C.I. Pigment Red 49:1; C.I. Pigment Violet 23; C.I.Pigment Green 7; C.I. Pigment Blue 61; C.I. Pigment Red 48:1; C.I.Pigment Red 52:1; C.I. Pigment Violet 1; C.I. Pigment White 6; C.I.Pigment Blue 15; C.I. Pigment Yellow 12; C.I. Pigment Blue 56; C.I.Pigment Orange 5; C.I. Pigment Black 7; C.I. Pigment Yellow 14; C.I.Pigment Red 48:2; and C.I. Pigment Blue 15:3;

(c) the aqueous ink is coated or printed onto a substrate selected frommetal foil, clay coated paper, glass, calendered paper, stainless paper,and films or other substrates of polyesters, polycarbonate, celluloseester, regenerated cellulose, poly(vinylidene chloride), polyamide,polyolefin, or polystyrene;

(d) the insolubilizing material is Al[CH--(COCH₃)₂ ]₃ ;

(e) the weight ratio of polyester to AcAc is from about 2,000/1 to about50/1; and

(f) a preferred group of metals wherein M is Al, Zr, Ni, Ca, V or Fe.

The complete chemical definitions of the above C.I. pigments are givenin the following table:

    ______________________________________                                        Pigments                                                                      Generic Name     C.A. Index/Chemical Name                                     ______________________________________                                        C.I. Pigment Yellow 17                                                                         Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]4,4'-                                                  diyl)bis(azo)bis[N--(2-meth                                                   oxyphenyl)-3-oxo-                                            C.I. Pigment Blue 27                                                                           Ferrate (4-1), hexakis                                                        (cyano-C)-ammonium iron                                                       (3+)(1:1:1)                                                  C.I. Pigment Red 49:2                                                                          1-Naphthalenesulfonic                                                         acid, 2-[(2-hydroxy-1-                                                        naphthalenyl)azo]-,                                                           calcium salt (2:1)                                           C.I. Pigment Red 81:1                                                                          Benzoic acid, 2,-[6-ethyl-                                                    amino)-3-(ethylimino)-2,7-                                                    dimethyl-3H--xanthen-9-yl]-,                                                  ethyl ester, w/molybdenum                                                     tungsten hydroxide oxide                                                      phosphate                                                    C.I. Pigment Red 81:3                                                                          Benzoic acid, 2-[6-ethyl-                                                     amino)-3-ethylimino)-2,7-                                                     dimethyl-3H--xanthen-9-yl]-,                                                  ethyl ester,                                                                  molybdatesilicate                                            C.I. Pigment Red 81:x                                                                          Benzoic acid, 2-[6-(ethyl-                                                    amino)-3-(ethylimino)-2,7-                                                    dimethyl-3H--xanthen-9-yl]-,                                                  ethyl ester,                                                                  molybdatephosphate                                           C.I. Pigment Yellow 83                                                                         Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)bis[N--                                                     (4-chloro-2,5-dimethoxy-                                                      phenyl)-3-oxo-                                               C.I. Pigment Red 57:1                                                                          2-Naphthalenecarboxylic                                                       acid, 3-hydroxy-4-[(4-                                                        methyl-2-sulfophenyl)azo]-,                                                   calcium salt (1:1)                                           C.I. Pigment Red 49:1                                                                          1-Naphthalenesulfonic                                                         acid, 2-[(2-hydroxy-1-                                                        naphthalenyl)azo]-,                                                           barium salt (2:1)                                            C.I. Pigment Violet 23                                                                         Diindolo[3,3',2'm]                                                            triphenodioxazine, 8,18-                                                      dichloro-5,15-diethyl-5,15-                                                   dihydro-                                                     C.I. Pigment Green 7                                                                           C.I. Pigment Green 7                                         C.I. Pigment Blue 61                                                                           Benzenesulfonic acid, [[4-                                                    [[4-phenylamino)phenyl]-                                                      [4-(phenylimino)-2,5-cyclo-                                                   hexadien-1-ylidene]methyl]-                                                   phenyl]amino]-                                               C.I. Pigment Red 48:1                                                                          2-Naphthalenecarboxylic                                                       acid, 4-[(5-chloro-4-                                                         methyl-2-sulfophenyl)azo]-                                                    3-hydroxy-, barium salt                                                       (1:1)                                                        C.I. Pigment Red 52:1                                                                          2-Naphthalenecarboxylic                                                       acid, 4-[(4-chloro-5-                                                         methyl-2-sulfophenyl)azo]-                                                    3-hydroxy-, calcium salt                                                      (1:1)                                                        C.I. Pigment Violet 1                                                                          Ethanaminium, N--[9-(2-                                                       carboxyphenyl)-6-(diethyl-                                                    amino)-3H--xanthen-3-                                                         ylidene]-N--ethyl-, molyb-                                                    datetungstatephosphate                                       C.I. Pigment White 6                                                                           Titanium oxide (TiO.sub.2)                                   C.I. Pigment Blue 15                                                                           Copper, [29H, 31H--                                                           phthalocyaninato (2-)-                                                        N.sup.29, N.sup.30, N.sup.31,                                                 N.sup.32 ]-, (Sp-4-1)-                                       C.I. Pigment Yellow 12                                                                         Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)]bis[3-                                                     oxo-N--phenyl-                                               C.I. Pigment Blue 56                                                                           Benzenesulfonic acid, 2-                                                      methyl-4-[[4-[[4-[(3-                                                         methylphenyl)amino]phenyl]-                                                   [4-[(3-methylphenyl)-                                                         imino]-2,5-cyclohexa-                                                         dien-1-ylidene]methyl]-                                                       phenyl]amino]-                                               C.I. Pigment Orange 5                                                                          2-Naphthalenol, 1-[(2,4-                                                      dinitrophenyl)azo]-                                          C.I. Pigment Black 7                                                                           Carbon black                                                 C.I. Pigment Yellow 14                                                                         Butanamide, 2,2'-[(3,3'-                                                      dichloro[1,1'-biphenyl]-                                                      4,4'-diyl)bis(azo)]bis-                                                       [N--(2-methylphenyl)-3-oxo-                                  C.I. Pigment Red 48:2                                                                          2-Naphthalenecarboxylic                                                       acid, 4-[(5-chloro-4-                                                         methyl-2-sulfophenyl)-                                                        azo]-3-hydroxy-, calcium                                                      salt (1:1)                                                   C.I. Pigment Blue 15:3                                                                         Copper, [29H, 31H--                                                           phthalocyaninato                                                              (2-)-N.sup.29, N.sup.30, N.sup.31,                                            N.sup.32 ]-, (SP-4-1)-                                       ______________________________________                                    

The inherent viscosities (I.V.) of the particular polyester materialsused herein range from about 0.1 to about 1.0 determined according toASTM D2857-70 procedure, in a Wagner Viscometer of Lab Glass, Inc. ofVineland, N.J., having a 1/2 mL capillary bulb, using a polymerconcentration about 0.25% by weight in 60/40 by weight ofphenol/tetrachloroethane. The procedure is carried out by heating thepolymer/solvent system at 120° C. for 15 minutes, cooling the solutionto 25° C. and measuring the time of flow at 25° C. The I.V. iscalculated from the equation ##EQU1## where: (n)=inherent viscosity at25° C. at a polymer concentration of 0.25 g/100 mL of solvent;

ln=natural logarithm;

t_(s) =sample flow time;

t_(o) =solvent-blank flow time; and

C=concentration of polymer in grams per 100 mL of solvent=0.25.

The units of the inherent viscosity throughout this application are indeciliters/gram. It is noted that higher concentrations of polymer,e.g., 0.50 g of polymer/100 mL solvent may be employed for more preciseI.V. determinations.

In general, the water-dispersible polyester materials useful in thepresent invention are excellent film formers for water based printinginks. The polymers form stable dispersions in water and produce tough,flexible films on drying. Films will form at temperatures down to justabove the freezing point of water. The polymers in dispersion form maybe plasticized if necessary, for example, with certain water immisciblephthalate esters to high degrees of flexibility. Printing inks from thepresent concentrates are readily further water reducible (dilution) andthe finished or press-ready inks typically comprise in % by weight, fromabout 30 to about 90% water, preferably from about 40 to about 70%, fromabout 4 to about 40% water-dispersible polymer, preferably from about 10to about 30%, and from about 0 to about 25% pigment, preferably fromabout 3 to about 20%. Various types of modifiers may be used such as upto about 15.0% by weight of polyvinyl alcohol or the like. The inks dryrapidly upon printing, wet surfaces exceptionally well and haveexcellent adhesion to many plastic films and metal foil as well as topaper, glass, polyethylene and many other substrates. Both the 100%solids, water-dispersible polymers and the corresponding aqueousdispersions thereof may be pigmented by conventional techniques, forexample, prior to the addition of the AcAc. The use of at leastsubstantially deionized water in the present invention is preferred inorder to prevent premature ion exchange.

The aforedescribed polyester material is prepared according to thepolyester preparation technology described in U.S. Pat. Nos.: 3,734,874;3,779,993; and 4,233,196, the disclosures of which are incorporatedherein by reference, and the use of the term "acid" in the abovedescription and in the appended claims includes the various esterforming or condensable derivatives of the acid reactants such as thedimethyl esters thereof as employed in the preparations set out in thesepatents. Among the preferred sulfo-monomers are those wherein thesulfonate group is attached to an aromatic nucleus such as benzene,naphthalene, diphenyl, or the like, or wherein the nucleus iscycloaliphatic such as in 1,4-cyclohexanedicarboxylic acid.

Dispersal of the present polyester material in water may be done, forexample, at preheated water temperature of about a 180° to about 200° F.and the polymer added as pellets to the vortex under high shearstirring. A Cowles Dissolver, Waring Blender, or similar equipment maybe used. Once water is heated to temperature, additional heat input isnot required. Depending upon the volume prepared, dispersal of thepellets by stirring should be complete within 15 to 30 minutes.Continued agitation with cooling may be desirable to prevent thickeningat the surface due to water evaporation. Viscosities of the dispersionsremain low up to nonvolatile levels of about 25-30%, but generallyincrease sharply above these levels. Viscosities of the dispersions willbe influenced by the degree of polymer dispersion (fineness) obtainedwhich is affected by the dispersing temperature, shear, and time.

The present concentrates and inks may also be prepared by milling, e.g.,two-roll milling the finely comminuted, nonpolymer soluble pigment andinsolubilizing agent into the solid polyester material, and for theaqueous inks and semiaqueous concentrates, thereafter dispersing themilled material to water in a manner generally similar to the proceduredescribed in U.S. Pat. No. 4,148,779 for solubilizing organic dispersetextile dyes in polyester for subsequent dispersal in water. Dispersionscan also be made by adding the pigment at high speed agitation to thepolyester material previously dispersed in water and then grinding in aball mill or sand mill to further reduce pigment size. The presence ofthe insolubilizing agent during this operation is preferred. Thepreferred pH of the present inks is from about 5.0 to about 7.5.

The viscosities of the inks may, of course, range widely, e.g. fromabout 15 to about 60 seconds as measured in a #2 Zahn cup according toASTM D-4212-82. The higher viscosities, e.g. from about 22 to about 60seconds and lower water levels, e.g. from about 10 to about 30%represent semiaqueous concentrated forms of the present inks. In thisregard, in order to reduce the viscosities of these inks when necessaryfor certain printing apparatus and processes varying amounts of waterare added. In this water addition, the ink viscosity may be reduced, forexample, up to about 60% or more of its original concentrate value, andthe press-ready ink viscosity preferably ranges between about 15 and 30seconds in a number 2 Zahn cup.

The following examples will further illustrate practice of theinvention.

EXAMPLE 1 Polyester Preparation

A mixture of 79.5 g (0.41 mole) of dimethyl isophthalate, 26.6 g (0.09mole) of dimethyl-5-sodiosulfoisophthalate, 54.1 g (0.51 mole) ofdiethylene glycol, 37.4 g (0.26 mole) of 1,4-cyclohexanedimethanol, 1.4mL of a 1.0% (based on Ti) catalyst solution of toitaniumtetraisopropoxide, and 0.74 g (0.009 mole) of sodium acetate buffer isstirred and heated for two hours at 200°-220° C. The temperature is thenraised to 275° C. and a vacuum of 0.3 mm is applied. Heating andstirring is continued for 1 hour under these conditions. After cooling,the polymer obtained has an I.V. of 0.36 and is tough and rubbery and isdissipatable in hot water to the extent of about 25 weight percent togive a clear, slightly viscous solution. The composition of the acidmoieties of this polyester material is analyzed to be 82 mole % ofisophthalic acid residue and 18 mole % 5 -sodiosulfoisophthalic acidresidue, and of the glycol moieties is analyzed to be 54 mole %diethylene glycol and 46 mole % 1,4-cyclohexandimethanol.

EXAMPLE 2

Polyesters designated (A), (B), (C) and (D) were prepared essentially inaccordance with Example 1 of the aforementioned U.S. Pat. No. 4,233,196from the following materials:

    ______________________________________                                        (A)                     g. moles                                              ______________________________________                                        Dimethyl Isophthalate (IPA)                                                                           0.415                                                 Dimethyl-5-Sodiosulfo-  0.085                                                 isophthalate (SIP)                                                            1,4-Cyclohexanedimethanol                                                                             0.520                                                 (CHDM)                                                                        Carbowax 1000 (CW 1000) 0.0273                                                Sodium Acetate          0.0085                                                Irganox 1010            0.1 wt. %                                             ______________________________________                                    

The Carbowax 1000 has the structure

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH

wherein n is about 22. The polymer analyzed by NMR contains (in reactedform) about 83 mole % IPA, about 17 mole % SIP, about 94.5 mole % CHDM,and about 5.5 mole % of CW 1000, and has an I.V. of about 0.39.

    ______________________________________                                        (B)                      g. moles                                             ______________________________________                                        Dimethyl Isophthalate    0.328                                                Dimethyl-5-Sodiosulfoisophthalate                                                                      0.072                                                1,4-Cyclohexanedimethanol                                                                              0.442                                                Carbowax 400 (n = 10)    0.058                                                Sodium Acetate           0.0072                                               ______________________________________                                    

The polymer as analyzed by NMR contains (in reacted form) about 82 mole% IRA, about 18 mole % SIP, about 85.5 mole % CHDM and about 14.5 mole %CW 400, and has an I.V. of about 0.46.

    ______________________________________                                        (C)                     g. moles                                              ______________________________________                                        Dimethyl Isophthalate   0.41                                                  Dimethyl-5-Sodiosulfoisophthalate                                                                     0.09                                                  1,4-Cyclohexanedimethanol                                                                             0.55                                                  Carbowax 400 (n = 90)   0.0005                                                Sodium Acetate          0.009                                                 ______________________________________                                    

The polymer as analyzed by NMR contains (in reacted form) about 82 mole% IPA, about 18 mole % SIP, about 99.9 mole % CHDM and about 0.1 mole %CW 4000, and has an I.V. of about 0.16.

    ______________________________________                                        (D)                     g. moles                                              ______________________________________                                        Dimethyl Isophthalate   0.205                                                 Dimethyl-5-Sodiosulfoisophthalate                                                                     0.045                                                 Ethylene Glycol (EG)    0.9638                                                Carbowax 2000 (n = 45)  0.03625                                               Sodium Acetate          0.0045                                                ______________________________________                                    

The polymer as analyzed by NMR contains (in reacted form) about 82 mole% IPA, about 18 mole % SIP, about 85.5 mole % EG, and about 14.5 mole %CW 2000, and has an I.V. of about 0.34.

In these polymers containing the Carbowax material, the n value ispreferably between about 6 and 150.

The present insolubilizing agents may be sequestered in the polymericmaterial by various means. A preferred method is to employ a volatilesolvent for the agent as described in the following example.

EXAMPLE 3

To 10 mL of an aqueous dispersion of the polyester of Example 1 (3.08 g.of polymer in 6.92 mL PG,19 of water) is added 0.51 gm ofAl(acetylacetonate)₃ in 2 mL of CH₂ Cl₂ and 2 mL of water. The mixtureis heated while distilling away the CH₂ Cl₂ and the final pottemperature is 95°-96° C. The resulting slurry is cooled and filtered togive a stable aqueous dispersion to which pigments or other additivescan be blended.

The acetylacetonates can also be added by stirring directly into theinks as shown in Example 4b below, and it is preferable to make theaddition as a solution of the acetylacetonate in a suitable solventwhich does not adversely affect the ink or its coatability.

In accordance with the present invention, inks prepared from polyestermaterial such as given in the above examples, and including the presentinsolubilizing agents and polymer insoluble pigments, with or withoutvarious property modifiers such as polyvinyl alcohol, Pluronics® or thelike have been found to be unexpectedly superior over prior aqueous inkswith respect to one or more of such properties as flow-out orprintability, final water resistance of the film, pigment wetting,pigment stability, temperature stability (heat and freeze-thaw),nonsettling for extended periods of time, nonpolluting with respect toodor and volatile organics, nonflocculating, wide viscosity range inks,adhesion to a variety of substrates, hardness, gloss, drying rate onsubstrates, resistance to grease, water and scuff, compatability withother water-based inks, wet rub resistance, ink mileage characteristics(considerable water dilution allowable at the press), ink pressstability in general, printability (clean, sharp transfer without"stringing or misting"), trapping, easy clean up, nonplugging ofprinting plates, flexibility, redispersibility or rewetting, crinkleresistance, high pigment loading, solvent resistance, alkali, chemicaland detergent resistance, blocking resistance, lightfastness, toughness,substrate wetting, hold-out, dry-rate, and no offset on the printingpress (coating, e.g., on tension rollers).

EXAMPLE 4a

    ______________________________________                                                         Approximate                                                  Ink (A)          % by Weight                                                  ______________________________________                                        Deionized Water  58.8                                                         Polymer of Example 1                                                                           19.2                                                         Raven 1020, Pigment                                                                            12.0                                                         n-Propanol       10.0                                                         ______________________________________                                    

The solid polymer (32 parts) is dispersed in approximately 68 parts ofdeionized water at 85° C. to 95° C. and 0.2 parts of biocide added. To75 parts of this dispersion is added 10 parts of deionized water and 15parts of the carbon black at high speed agitation for five minutes on aWaring Blender. The mixture is then milled in an Eiger mill operated atabout 5,000 rpm for about 7.5 minutes to further reduce the pigment fora grind of, for example, from about "2" to about "0" NPIRI grind gauge.The resulting composition has a pH of about 5.6 and a viscosity of 26-29seconds on a #2 Zahn cup determined according to ASTM D-4212-82. To 90parts by weight of this composition is added 10 parts by weight ofn-propanol with stirring. This procedure yields an aqueous-alcohol ink(A) which is nonsettling for extended periods, does not flocculate oragglomerate, and can be reduced in viscosity with deionized water. Theink dries rapidly upon printing, has virtually no odor and can bereadily cleaned from printing equipment with warm deionized water.Tenacious, dried films of this ink can be cleaned from printingequipment with small amounts of detergents (5-10%) added to warm(80°-90° F.) deionized water. Such properties are also obtained usingother pigments such as those disclosed above.

EXAMPLE 4b Ink (B)

To 5.0 gm of ink (A) is added with stirring, 0.2 gm of 2.0% by weightAl(acetylacetonate)₃ in n-propanol. This procedure yields anaqueous-alcohol ink (B) essentially similar to ink (A) above and whichis also nonsettling for extended periods, does not flocculate oragglomerate, can be reduced in viscosity with deionized water, driesrapidly upon printing, has virtually no odor, and can be readily cleanedfrom printing equipment with warm deionized water. Proofs of this inkare prepared with a flexographic hand proofer employing a 180-lineanilox roll on aluminum foil, Mylar film, corona discharge treatedpolyethylene coated paperboard and corona discharge treated polyethylenefilm with excellent adhesion and printability results.

At this point, the differences in the two inks, (A) and (B), becomemanifest. Whereas tenacious, dried films of ink (A) can be cleaned fromprinting equipment with small amounts of detergents (5-10%) added towarm (80°-90° F.) deionized water, dried films of ink (B) especiallythose which have been aged, exhibit greater resistance to waterredispersibility through the operation of the acetylacetonates.

The point of drying of the present ink films beyond which waterredispersibility becomes impractical is at water contents of the inkfilm of less than about 0.1%, preferably less than about 0.01% by weightof water based on total ink film weight. At lower water concentrationsthe solubilizing capacity of the cationic sulfo groups is essentiallylost, presumably through ion exchange with the acetylacetonatemultivalent cation.

The sequestering and insolubilizing phenomena observed above is typicalfor all of the water-dispersible polymeric materials generally disclosedherein and specifically disclosed in the examples, and it must be notedthat as in all such complex systems, variations in the effect of thepresent invention on different ink systems coming within the broaddefinitions herein, must be expected.

The weight percentages of the polyester, water, cosolvent, and pigmentwill of course vary depending on wehther it is desired to produce asubstantially dry concentrate, an intermediate aqueous concentrate, or afinished, press-ready, aqueous ink, all of which contain theacetylacetonates. Typical approximate ranges, Broad (1), Preferred (2),and Most Preferred (3), of these percentages (dry wt. %) are given inthe following table.

    __________________________________________________________________________                   Intermediate                                                   Finished       Aqueous  Substantially                                         Ink            Concentrate                                                                            Dry Concentrate                                       1        2  3  1  2  3  1   2   3                                             __________________________________________________________________________    Polyester                                                                           4- 10-                                                                              15-                                                                              23-                                                                              40-                                                                              49-                                                                              90.0-                                                                             34.0-                                                                             47.0-                                               40 30 25 90 80 72 99.9                                                                              94.6                                                                              89.0                                          H.sub.2 O                                                                           30-                                                                              40-                                                                              50-                                                                              10-                                                                              15-                                                                              18-                                                                              0.01-                                                                             0.4-                                                                              1.0-                                                90 70 65 30 25 23 10  6.0 3.0                                           Cosolvent                                                                           0- 0- 2- 0- 0- 0- <0.01                                                                             <0.01                                                                             <0.01                                               15 10 7  7  5  3                                                        Pigment                                                                             0- 3- 5- 0- 5- 10-                                                                              0-  5-  10-                                                 25 20 15 40 30 25 70  60  50                                            __________________________________________________________________________

In these compositions, the concentrations of the acetylacetonates (AcAc)are expressed in terms of the weight ratios of polyester/AcAc and rangebroadly from about 10,000/1 to about 10/1, preferably from about 2,000/1to about 50/1, and most preferably from 1,500/1 to about 200/1.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. A composition useful as a printing ink or useful for thepreparation of a printing ink, comprising a substantially homogeneoussystem of the components:(1) from about 4 to about 90 weight % ofpolymeric material of at least one linear, water-dispersible polymerhaving carbonyloxy linking groups in the linear molecular structurewherein up to 80% of the linking groups may be carbonylamido linkinggroups, the polymer having an inherent viscosity of from about 0.1 toabout 1.0 measured in a 60/40 parts by weight solution ofphenol/tetrachloroethane at 25° C. and at a concentration of 0.25 gramof polymer in 100 mL of the solvent, the polymer containingsubstantially equimolar proportions of acid equivalents (100 molepercent) to hydroxy and amino equivalents (100 mole percent), thepolymer comprising the reaction products of (a), (b), (c) and (d) fromthe following reactants or ester forming or esteramide formingderivatives thereof;(a) at least one difunctional dicarboxylic acid; (b)from about 4 to about 25 mole percent, based on a total of all acid,hydroxyl and amino equivalents being equal to 200 mole percent, of atleast one difunctional sulfomonomer containing at least one cationicsulfonate group attached to an aromatic or cycloaliphatic nucleuswherein the functional groups are hydroxy, carboxyl or amino; (c) atleast one difunctional reactant selected from a glycol or a mixture of aglycol and diamine having two --NRH groups, the glycol containing two--CH₂ --OH groups of which(1) at least 15 mole percent based on thetotal mole percent of hydroxy or hydroxy and amino equivalents, is apoly(ethylene glycol) having the structural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of from 2 to about 20, or (2) of which from about 0.1to less than about 15 mole percent based on the total mole percent ofhydroxy or hydroxy and amino equivalents, is a poly(ethylene glycol)having the structural formula

    H--OCH.sub.2 --CH.sub.2 --.sub.n OH,

n being an integer of between 2 and about 500, and with the proviso thatthe mole percent of said poly(ethylene glycol) within said range isinversely proportional to the quantity of n within said range; and (d)from none to at least one difunctional reactant selected from ahydroxy-carboxylic acid having one --C(R)₂ --OH group, anaminocarboxylic acid having one --NRH group, and an amino-alcohol havingone --C(R)₂ --OH group and one --NRH group, or mixtures of saiddifunctional reactants; wherein each R in the (c) or (d) reactants is aH atom or an alkyl group of 1 to 4 carbon atoms; (2) from none to about70 weight % of pigment material; (3) from about 0.01 to about 90 weight% of water; and (4) one or more acetylacetonates of the formulaM[CH--(COCH₃)₂ ]_(n) wherein M is a polyvalent metal and n is thechemical valence of M, the weight ratio of polyester to totalacetylacetonates being from about 10,000/1 to about 10/1.
 2. Thecomposition of claim 1 wherein the n value of reactant (c)(2) of theformula H--OCH₂ --CH₂)_(n) OH is between 2 and about
 200. 3. Thecomposition according to claim 2 wherein the polymeric materialcomprises one or more polyester materials having an inherent viscosityof from about 0.28 to about 0.38, an acid moiety of from about 75 toabout 84 mole % isophthalic acid and conversely from about 25 to about16 mole % 5-sodiosulfoisophthalic acid, and a glycol moiety of fromabout 45 to about 60 mole % diethylene glycol and conversely from about55 to about 44 mole % 1,4-cyclohexanedimethanol or ethylene glycol ormixtures thereof, and the pigment material is present in a weight ratiowith respect to total polyester materials of from about 1/10 to about2/1.
 4. The composition according to claim 3 wherein said acid moietycomprises from about 80 to about 83 mole % isophthalic acid andconversely from about 20 to about 17 mole % 5-sodiosulfoisophthalicacid, and said glycol moiety comprises from about 52 to about 56 mole %diethylene glycol and conversely from about 48 to about 44 mole %1,4-cyclohexanedimethanol.
 5. The composition according to claim 4wherein the weight ratio of polyester to acetylacetonates is from about1,500/1 to about 200/1, and the metal M is selected from Al, Zr, Ni, Ca,V, or Fe.
 6. The composition according to any one of claims 1-5 whereinthe pigment is one or a mixture of the following color index materails:C.I. Pigment Yellow 17; C.I. Pigment Blue 27; C.I. Pigment Red 49:2;C.I. Pigment Red 81:1; C.I. Pigment Red 81:3; C.I. Pigment Red 81:x;C.I. Pigment Yellow 83; C.I. Pigment Red 57:1; C.I. Pigment Red 49:1;C.I. Pigment Violet 23; C.I. Pigment Green 7; C.I. Pigment Blue 61; C.I.Pigment Red 48:1; C.I. Pigment Red 52:1; C.I. Pigment Violet 1; C.I.Pigment White 6; C.I. Pigment Blue 15; C.I. Pigment Yellow 12; C.I.Pigment Blue 56; C.I. Pigment Orange 5; C.I. Pigment Black 7; C.I.Pigment Yellow 14; C.I. Pigment Red 48:2; and C.I. Pigment Blue 15:3. 7.The composition of claim 6 wherein the polyester material comprises fromabout 10 to about 30 weight %, the pigment material comprises from about3 to about 20 weight %, the water comprises from about 40 to about 70weight %, and the weight ratio of polyester to acetylacetonates is fromabout 2,000/1 to about 50/1.
 8. The composition of claim 6 wherein thepolyester material comprises from about 15 to about 25 weight %, thepigment material comprises from about 5 to about 15 weight %, the watercomprises from about 50 to about 65 weight %, and the weight ratio ofpolyester to acetylacetonates is from about 1,500/1 to about 200/1. 9.The composition of claim 6 coated onto a substrate selected from metalfoil, bleached and unbleached Kraft paper, clay coated paper, stainlesspaper, and films or other substrates of polyester, polycarbonate,cellulose ester, regenerated cellulose, poly(vinylidiene chloride),polyamide, polyolefin, or polystyrene.
 10. A substantiallywater-insoluble coating or print on a substrate according to claim 9wherein substantially all water has evaporated, with or without theapplication of heat, and a substantial portion of the initial metalcations of the water solubilizing sulfonate groups of the polymericmaterial has been replaced with an insolubilizing cation.
 11. The methodfor preparing the aqueous composition of claim 1 comprising the stepsof:(a) dispersing said polymeric material in water; (b) adding saidinsolublizing agent to the dispersion of (a) with agitation to obtain asubstantially homogeneous mixture; (c) adding said pigment to themixture of (b) with agitation to form a pre-dispersion blend; and (d)grinding the blend of (c) to reduce the pigment particle size to lessthan about 6.0 on the NPIRI scale.